Extraordinary Properties of Alcohols from the Homologous Series of Methanol
Keywords:monohydric primary alcohols, density, optical and dielectric properties
Non-trivial properties of thermodynamic quantities such as the density, the critical and triple point temperatures, and their ratio, as well as the optical and dielectric properties, have been analyzed for primary alcohols from the methanol series. The aim is to reveal relationships among their values measured at the same temperatures for alcohols with different ordinal numbers m’s in the methanol series. It is shown that the non-monotonic character of the temperature dependences of alcohol densities is associated with methanol rather than ethanol, as may seem at first glance. The critical temperature of methanol also deviates from the quasilinear dependence of the critical alcohol temperatures on m. With the growing m, the ratio between the critical and triple-point temperatures for alcohols is shown to tend to the corresponding value for water. Simple linear dependences of the electronic and effective static polarizabilities of alcohol molecules on m are established. The transverse and longitudinal components of the polarizability tensor for alcohol molecules are found. The dipole moments of the closest neighbor molecules in the alcohols are proved to anticorrelate, i.e. to orient in opposite directions.
P. Golub, I. Doroshenko, V. Pogorelov. Quantum-chemical modeling of energy parameters and vibrational spectra of chain and cyclic clusters of monohydric alcohols. Phys. Lett. A 378, 1937 (2014). https://doi.org/10.1016/j.physleta.2014.04.032
V.N. Stabnikov, I.M. Roiter, T.B. Protsyuk. Ethyl Alcohol (Pishchevaya Promyshlennost, 1976) (in Russian).
A Brief Handbook of Physicochemical Values. Edited by A.A. Ravdel', A.M. Ponomareva (Spetsialnaya Literatura, 1998) (in Russian).
Chemist's Handbook, Vol. 1 (Khimiya, 1982) (in Russian).
Tables of Physical Quantities. Edited by I.K. Kikoin. (Atomizdat, 1976) (in Russian).
M.M. Karavaev, V.E. Leonov, I.G. Popov, E.T. Shepelev. Technology of Synthetic Methanol (Khimiya, 1984) (in Russian).
V. Pogorelov, L. Bulavin, I. Doroshenko, O. Fesjun, O. Veretennikov. The structure of liquid alcohols and the temperature dependence of vibrational bandwidth. J. Mol. Struct. 708, 61 (2004). https://doi.org/10.1016/j.molstruc.2004.03.003
V. Pogorelov, A. Yevglevsky, I. Doroshenko, L. Berezovchuk, Yu. Zhovtobryuch. Nanoscale molecular clusters and vibrational relaxation in simple alcohols. Superlat. Microstruct. 44, 571 (2008). https://doi.org/10.1016/j.spmi.2008.01.014
T.V. Lokotosh, N.P. Malomuzh, V.L. Zakharchenko. Anomalous density and permittivity effects on the structure of water. J. Struct. Chem. 44, 1001 (2003). https://doi.org/10.1023/B:JORY.0000034807.32927.58
N.P. Malomuzh, A.V. Oleinik. Nature of the kinematic shear viscosity of water. J. Struct. Chem. 49, 1055 (2008). https://doi.org/10.1007/s10947-008-0178-1
A.I. Fisenko, N.P. Malomuzh, A.V. Oleynik. To what extent are thermodynamic properties of water argon-like? Chem. Phys. Lett. 450, 297 (2008). https://doi.org/10.1016/j.cplett.2007.11.036
M. Born, E. Wolf. Principles of Optics (Cambridge Univ. Press, 1999).
V.Ya. Gotsul'skii, N.P. Malomuzh, V.E. Chechko. Properties of hydrogen bonds in water and monohydric alcohols. Russ. J. Phys. Chem. A 92, 1516 (2018). https://doi.org/10.1134/S0036024418080149
V.E. Chechko, V.Ya. Gotsulsky, N.P. Malomuzh. Surprising thermodynamic properties of alcohols and water on their coexistence curves. J. Mol. Liq. 272, 590 (2018). https://doi.org/10.1016/j.molliq.2018.09.126
V.Ya. Gotsul'skii, N.P. Malomuzh, V.E. Chechko. The role of two-particle effects in the behavior of refraction of single-component liquids and two-component solutions. Opt. Spectrosc. 120, 615 (2016). https://doi.org/10.1134/S0030400X16030103
D.S. Eisenberg, W. Kauzmann. The Structure and Properties of Water (Oxford Univ. Press, 2005) (ISBN: 0198570260, 9780198570264). https://doi.org/10.1093/acprof:oso/9780198570264.001.0001
D.W. Davidson. The dielectric properties of methanol and methanol-d. Can. J. Chem. 35, 458 (1957). https://doi.org/10.1139/v57-066
R.M. Shirke, A. Chaudhari, N.M. More, P.B. Patil. Dielectric measurements on methyl acetate + alcohol mixtures at (288, 298, 308, and 318) K using the time domain technique. J. Chem. Eng. Data 45, 917 (2000). https://doi.org/10.1021/je000066+
R.M. Shirke, A. Chaudhari, N.M. More, P.B. Patil. Temperature dependent dielectric relaxation study of ethyl acetate - alcohol mixtures using time domain technique. J. Mol. Liq. 94, 27 (2001). https://doi.org/10.1016/S0167-7322(01)00239-2
M.T. Khimenko, V.V. Aleksandrov, N.N. Gritsenko. Polarizability and radii of molecules of some pure liquids. Zh. Fiz. Khim. 47, 2914 (1973) (in Russian).
V.A. Granzhan, O.G. Kirillova. Physico-chemical study of N-methyl-2-pyrrolidone-methanol system. Zh. Prikl. Khim. 43, 1875 (1970) (in Russian).
F.X. Hasslon, R.H. Cole. Dielectric properties of liquid ethanol and 2-propanol. J. Chem. Phys. 23, 1756 (1955). https://doi.org/10.1063/1.1740575
V.N. Makhlaichuk, N.P. Malomuzh. Manifestation of cluster excitations in dielectric properties of water vapor and liquid water as well as their heat capacity. J. Mol. Liq. 253, 83 (2018). https://doi.org/10.1016/j.molliq.2018.01.018
N.P. Malomuzh, V.M. Makhlaichuk. Dimerization degree of water molecules, their effective polarizability, and heat capacity of saturated water vapor. Ukr. J. Phys. 63, 121 (2018). https://doi.org/10.15407/ujpe63.2.121
J.G. Kirkwood. Theory of solutions of molecules containing widely separated charges with special application to zwitterions. J. Chem. Phys. 2, 351 (1934). https://doi.org/10.1063/1.1749489
I.E. Tamm. Fundamentals of the Theory of Electricity (Mir, 1979).
O.A. Osipov, V.I. Minkin, A.D. Garnovskii. Handbook on Dipole Moments (Vysshaya Shkola, 1971) (in Russian).
P. Venkateswarlu, W. Gordy. Methyl alcohol II. Molecular structure. J. Chem. Phys. 23, 1200 (1955). https://doi.org/10.1063/1.1742240
L.D. Landau, E.M. Lifshitz. Statistical Physics (Butterworth-Heinemann, 1980) [ISBN: 978-0-7506-3372-7].
M. Gude, A.S. Teja. Vapor-liquid critical properties of elements and compounds. 4. Aliphatic alkanols. J. Chem. Eng. Data 40, 1025 (1995). https://doi.org/10.1021/je00021a001
R.C. Wilhoit, J.Chao, K.R. Hall. Thermodynamic properties of key organic compounds in the carbon range C1 to C4. Part 1. Properties of condensed phases. J. Phys. Chem. Ref. Data 14, 1 (1985). https://doi.org/10.1063/1.555747
J.F. Counsell, J.L. Hales, J.F. Martin. Thermodynamic properties of organic oxygen compounds. Part 16. Butyl alcohol. Trans. Faraday Soc. 61, 1869 (1965). https://doi.org/10.1039/TF9656101869
G.S. Parks, H.M. Huffman, M. Barmore. Thermal data on organic compounds. XI. The heat capacities, entropies and free energies of ten compounds containing oxygen or nitrogen. J. Am. Chem. Soc. 55, 7, 2733 (1933). https://doi.org/10.1021/ja01334a016
K.K. Kelley. The heat capacities of ethyl and hexyl alcohols from 16 to 298 K and the corresponding entropies and free energies. J. Am. Chem. Soc. 51, 779 (1929). https://doi.org/10.1021/ja01378a016
G.S. Parks, W.D. Kennedy, R.R. Gates, J.R. Mosley, G.E. Moore, M.L. Renquist. Thermal data on organic compounds XXVI. Some heat capacity, entropy and free energy data for seven compounds containing oxygen. J. Am. Chem. Soc. 78, 56 (1956). https://doi.org/10.1021/ja01582a015
C. Spizzichino. Contribution a l'etude des tensions de vapeur et des chaleurs de vaporisation des acides gras, esters methyliques et alcools gras a des pressions inferieures a 1 mm de mercure. J. Recherch. CNRS 34, 1 (1956).
How to Cite
License to Publish the Paper
The corresponding author and the co-authors (hereon referred to as the Author(s)) of the paper being submitted to the Ukrainian Journal of Physics (hereon referred to as the Paper) from one side and the Bogolyubov Institute for Theoretical Physics, National Academy of Sciences of Ukraine, represented by its Director (hereon referred to as the Publisher) from the other side have come to the following Agreement:
1. Subject of the Agreement.
The Author(s) grant(s) the Publisher the free non-exclusive right to use the Paper (of scientific, technical, or any other content) according to the terms and conditions defined by this Agreement.
2. The ways of using the Paper.
2.1. The Author(s) grant(s) the Publisher the right to use the Paper as follows.
2.1.1. To publish the Paper in the Ukrainian Journal of Physics (hereon referred to as the Journal) in original language and translated into English (the copy of the Paper approved by the Author(s) and the Publisher and accepted for publication is a constitutive part of this License Agreement).
2.1.2. To edit, adapt, and correct the Paper by approval of the Author(s).
2.1.3. To translate the Paper in the case when the Paper is written in a language different from that adopted in the Journal.
2.2. If the Author(s) has(ve) an intent to use the Paper in any other way, e.g., to publish the translated version of the Paper (except for the case defined by Section 2.1.3 of this Agreement), to post the full Paper or any its part on the web, to publish the Paper in any other editions, to include the Paper or any its part in other collections, anthologies, encyclopaedias, etc., the Author(s) should get a written permission from the Publisher.
3. License territory.
The Author(s) grant(s) the Publisher the right to use the Paper as regulated by sections 2.1.1–2.1.3 of this Agreement on the territory of Ukraine and to distribute the Paper as indispensable part of the Journal on the territory of Ukraine and other countries by means of subscription, sales, and free transfer to a third party.
4.1. This Agreement is valid starting from the date of signature and acts for the entire period of the existence of the Journal.
5.1. The Author(s) warrant(s) the Publisher that:
– he/she is the true author (co-author) of the Paper;
– copyright on the Paper was not transferred to any other party;
– the Paper has never been published before and will not be published in any other media before it is published by the Publisher (see also section 2.2);
– the Author(s) do(es) not violate any intellectual property right of other parties. If the Paper includes some materials of other parties, except for citations whose length is regulated by the scientific, informational, or critical character of the Paper, the use of such materials is in compliance with the regulations of the international law and the law of Ukraine.
6. Requisites and signatures of the Parties.
Publisher: Bogolyubov Institute for Theoretical Physics, National Academy of Sciences of Ukraine.
Address: Ukraine, Kyiv, Metrolohichna Str. 14-b.
Author: Electronic signature on behalf and with endorsement of all co-authors.